Fabric care compositions

ABSTRACT

There is provided a method for preventing or reducing the fading of colour on fabric by means of a divalent salt. Compositions which provide care to the color of fabrics and comprising a dye fixing agent and the divalent salt are also herein provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.09/762,081, filed Feb. 1, 2001 (Attorney Docket No. CM1883), whichclaims priority under 35 U.S.C. § 119(a) to European Application SerialNo. 98870174.4, filed Aug. 3, 1998 (Attorney Docket No. CM1883F).

TECHNICAL FIELD OF THE INVENTION

There is provided a composition which provides care to the treatedfabrics, in particular color protection, especially after multiple washcycles.

BACKGROUND OF THE INVENTION

The domestic treatment of colored fabric is a problem known in the artto the formulator of laundry compositions. Hence, It is well known thatalternating cycles of using and laundering fabrics and textiles, such asarticles of worn clothing and apparel, will inevitably adversely affectthe appearance and integrity of the fabric and textile items so used andlaundered. Fabrics and textiles simply wear out over time and with use.Laundering of fabrics and textiles is necessary to remove soils andstains which accumulate therein and thereon during ordinary use.However, the laundering operation itself, over many cycles, canaccentuate and contribute to the deterioration of the integrity and theappearance of such fabrics and textiles.

Deterioration of fabric integrity and appearance can manifest itself inseveral ways. Short fibers are dislodged from woven and knitfabric/textile structures by the mechanical action of laundering. Thesedislodged fibers may form lint, fuzz or “pills” which are visible on thesurface of fabrics and diminish the appearance of newness of the fabric.Further, repeated laundering of fabrics and textiles, especially withbleach-containing laundry products, can remove dye from fabrics andtextiles and impart a faded, worn out appearance as a result ofdiminished color intensity, and in many cases, as a result of changes inhues or shades of color.

Accordingly, the problem of formulating laundry compositions whichreduces the amount of dyes released from coloured fabrics upon wettreatment is a particular challenge to the formulator. This problem isnow even more acute with the trends of consumers to move towards morecolored fabrics.

Numerous solutions have been proposed in the art to solve this problemsuch as by treating the fabric with a dye scavenger during the washingprocess as exemplified by EP 0,341,205, EP 0,033,815 or with a polyvinylsubstance as exemplified by WO 94/11482. However, all these solutionsare focused on preventing the end result of the dye bleeding, that isthe redeposition of the dye on the fabrics. It is now an object of theinvention to take the problem of dye at one of its source, that is tothe colour fading arising from the bleeding of the dye due to its poorfabric substantivity, especially after multiple washings.

Solutions may be found for use in the industrial treatments. However,these solutions are not usually transposable to domestic treatments.Indeed, in industrial processes a strict control over parameters such aspH, electrolyte concentration, water hardness, temperature, etc. ispossible whereas in a domestic washing machine, such a high level ofcontrol is not possible.

In addition, in a domestic process, and in particular in a domesticrinse process, it is not practical to rely on high treatmenttemperatures such as those used in industrial processes, that is ofabove 40° C. Furthermore, industrial processes use high concentrationsof fixing agents which is required for industrial scale treatment whilstfor domestic treatment a low level is most preferred for economicalreasons.

Accordingly, notwithstanding the advances in the art, there is still aneed for an efficient and economical composition which provideseffective reduction of the amount of dyes released from colored fabricsupon subsequent wet domestic treatments.

EP462806 provides the use of a cationic dye fixing agent in domestictreatment which assist in binding the loosely held dye to the fabric.However, whilst efficient, it has been found that the fading of fabricsstill occurred to a certain degree, especially after multiple washcycles.

Accordingly, it is therefore an advantage of the invention to providecompositions with effective dye fixing properties.

Another advantage of the invention is that such compositions provide asynergistic increase in performance of the above mentioned benefit.

A further advantage of the invention is that the treated fabrics willthereafter show a reduced tendency in the subsequent wash to releasedye. Such benefit is more particularly seen after multi-wash cycles(e.g. 20 wash cycles).

SUMMARY OF THE INVENTION

The present invention relates to a colour care composition comprising adye fixing agent and a divalent salt.

In another aspect of the invention, there is provided the use and methodthereof for preventing or reducing the colour fading of fabrics by meansof the divalent salt.

Dye Fixing Agent

Dye fixing agent is an essential component of the invention composition.Dye fixing agents, or “fixatives”, are well-known, commerciallyavailable materials which are designed to improve the appearance of dyedfabrics by minimizing the loss of dye from fabrics due to washing. Notincluded within this definition are components which are fabricsofteners or those described hereinafter as amino-functional polymers.

Many dye fixing agents are cationic, and are based on variousquaternized or otherwise cationically charged organic nitrogencompounds. Cationic fixatives are available under various trade namesfrom several suppliers. Representative examples include: CROSCOLOR PMF(July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No.8544) from Crosfield; INDOSOL E-50 (Feb. 27, 1984, Ref No. 6008.35.84;polyethyleneamine-based) from Sandoz; SANDOFIX TPS, which is alsoavailable from Sandoz and is a preferred polycationic fixative for useherein and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWINSRF-O and REWIN DWR from CHT-Beitlich GMBH, Tinofix® ECO, Tinofix®FRDand Solfin® available from Ciba-Geigy.

Other cationic dye fixing agents are described in “Aftertreatments forimproving the fastness of dyes on textile fibres” by Christopher C. Cook(REV. PROG. COLORATION Vol. 12, 1982). Dye fixing agents suitable foruse in the present invention are ammonium compounds such as fattyacid—diamine condensates e.g. the hydrochloride, acetate, metosulphateand benzyl hydrochloride of oleyldiethyl aminoethylamide,oleylmethyl-diethylenediaminemethosulphate, monostearyl-ethylenediaminotrimethylammonium methosulphate and oxidized products of tertiaryamines; derivatives of polymeric alkyldiamines, polyamine-cyanuricchloride condensates and aminated glycerol dichlorohydrins.

Preferred dye fixing agents are the cellulose reactive dye fixingagents.

By “cellulose reactive dye fixing agent”, it is meant that the agentreacts with the cellulose fibers upon heat treatment. The agentssuitable for use herein can be defined by the following test procedure,so called cellulose reactivity test measurement.

Cellulose Reactivity Test Measurement

Two pieces of bleeding fabrics (e.g. 10×10 cm of knitted cotton dyedwith Direct Red 80) are soaked for 20 minutes in an aqueous solution of1% (w/w) of the cellulose reactive dye fixing agent candidate. The pH ofthe solution is as it is obtained at this concentration.

The swatches are then dried. One of the dried swatches as well as anunsoaked swatch (control 1) are passed 10 times trough an ironingcalender set on a linen setting.

A control 2 swatch is also used in this measurement test which is anon-soaked and non-ironed swatch.

The 4 swatches are washed separately in Launder-o-meter pots undertypical conditions with a commercial detergent used at the recommendeddosage for ½ hour at 60° C., followed by a thorough rinsing of 4 times200 ml of cold water and then line dried.

The wash-fastness is then measured on the swatches by determination oftheir so-called delta-E values versus a new, untreated swatch. Delta E'sare defined, for instance, in ASTM D2244. Delta E is the computed colordifference as defined in ASTM D2244, i.e the magnitude and direction ofthe difference between two psychophysical color stimuli defined bytristimulus values, or by chromaticity coordinates and luminance factor,as computed by means of a specified set of color-difference equationsdefined in the CIE 1976 CIELAB opponent-color space, the Hunteropponent-color space, the Friele-Mac Adam-Chickering color space or anyequivalent color space.

Accordingly, the lower the Delta E versus new, the better the washfastness improvement.

If the washfastness improvement of the ironed-soaked swatch is betterthan that of the non-ironed soak swatch and also better than the tworespective control 1 and 2, then the candidate is a cellulose reactivedye fixing agent for the purpose of the invention.

Typical cellulose reactive dye fixing agents are products containing thereactive group of the reactive dye classes selected fromhalogeno-triazine products, vinyl sulphones compounds, epichlorhydrinederivatives, hydroxyethylene urea derivatives, formaldehyde condensationproducts, polycarboxylates, glyoxal and glutaraldehyde derivatives andmixtures thereof.

Other reactive functionalities for cellulose can be found in Textileprocessing and properties. Elsevier (1997) from Tyrone L. Vigo at page120 to 121, which provides the use of specific electrophilic groups withcellulose affinity.

Preferred hydroxyethylene urea derivatives includedimethyloldihydroxyethylene, urea, and dimethyl urea glyoxal.

Preferred formaldehyde condensation products include the condensationproducts derived from formaldehyde and a group selected from anamino-group, an imino-group, a phenol group, an urea group, a cyanamidegroup and an aromatic group. Commercially available compounds among thisclass are Sandofix WE 56 from Clariant, Zetex E from Zeneca and LevogenBF from Bayer.

Preferred polycarboxylates derivatives include butane tetracarboxilicacid derivatives, citric acid derivatives, polyacrylates and derivativesthereof.

A most preferred cellulosic reactive dye fixing agents is one of thehydroxyethylene urea derivatives class commercialised under thetradename of Indosol CR from Clariant. Still other most preferredcellulosic reactive dye fixing agents are commercialised under thetradename Rewin DWR and Rewin WBS from CHT R. Beitlich.

Among the dye fixing agents disclosed, the preferred agent for use inthe present invention are cationic, in particular polycationic dyefixing agents.

A typical amount of the dye fixing agent to be employed in thecomposition of the invention is from 0.01% to 50% by weight, preferablyfrom 0.01% to 25% by weight, more preferably from 1% to 10% by weight,most preferably from 1.5% to 5% active by weight of the composition.

Divalent Salt

A divalent salt is an essential ingredient of the invention. By use ofthis ingredient, the fabric appearance, in particular the colorprotection of the fabrics, is improved. Not to be bound by theory, it isbelieved that the salt acts by reducing the dye solubility.

A divalent salt is defined as a salt which in water dissociates andreleases a metal ion with a valence of two.

The salt useful in the present invention is made of earth alkalinemetal, and is a compound that can form hydrates upon crystallization.Typically, the salt for use in the present invention have the followingformula: AM; wherein A is a cation. This cation is an earth alkalinemetal, preferably selected from magnesium, calcium, more preferablymagnesium, and wherein M is a couteranion selected from sulfate,chloride, nitrate, carbonate, borate, and carboxylates.

Preferred salts are salts selected from magnesium, calcium and mixturesthereof; more preferably salt of magnesium.

Particularly preferred salts for use herein are selected from magnesiumsulphate, magnesium bicarbonate, magnesium chloride, magnesium borate,magnesium citrate, and mixtures thereof, more preferably are selectedfrom magnesium sulphate, magnesium chloride and mixtures thereof.

A typical amount of the divalent salt to be employed in the compositionof the invention is from 0.01% to 90% by weight, preferably from 0.5%and 90%, more preferably between 1% and 20%, most preferably between 3%and 10%, by weight of the composition.

For the purpose of the invention, it is preferred to have a weight ratioof the divalent salt to dye fixing agent greater than 1:1.

Colour Care Component

The fabric care compositions may also comprise one or more of thefollowing colour care component:

Amino-functional Polymer

Amino-functional polymers advantageously provide care to the colors offabrics. Not included within this definition are components which arepolymers as defined herein before or those described hereinafter as dyefixing agents.

The amino-functional polymers suitable for use in the present inventionare water-soluble or dispersible, polyamines. Typically, theamino-functional polymers for use herein have a molecular weight between150 and 10⁶, preferably between 600 and 20,000, most preferably between1000 and 10,000. These polyamines comprise backbones that can be eitherlinear or cyclic. The polyamine backbones can also comprise polyaminebranching chains to a greater or lesser degree. Preferably, thepolyamine backbones described herein are modified in such a manner thatat least one, preferably each nitrogen of the polyamine chain isthereafter described in terms of a unit that is substituted,quaternized, oxidized, or combinations thereof.

For the purposes of the present invention the term “modification” as itrelates to the chemical structure of the polyamines is defined asreplacing a backbone —NH hydrogen atom by an R′ unit (substitution),quaternizing a backbone nitrogen (quaternized) or oxidizing a backbonenitrogen to the N-oxide (oxidized). The terms “modification” and“substitution” are used interchangably when referring to the process ofreplacing a hydrogen atom attached to a backbone nitrogen with an R′unit. Quaternization or oxidation may take place in some circumstanceswithout substitution, but substitution is preferably accompanied byoxidation or quaternization of at least one backbone nitrogen.

The linear or non-cyclic polyamine backbones that comprise theamino-functional polymer have the general formula:

The cyclic polyamine backbones that comprise the amino-functionalpolymer have the general formula:

The above backbones prior to optional but preferred subsequentmodification, comprise primary, secondary and tertiary amine nitrogensconnected by R “linking” units

For the purpose of the present invention, primary amine nitrogenscomprising the backbone or branching chain once modified are defined asV or Z “terminal” units. For example, when a primary amine moiety,located at the end of the main polyamine backbone or branching chainhaving the structureH₂N-[R]-is modified according to the present invention, it is thereafter definedas a V “terminal” unit, or simply a V unit. However, for the purposes ofthe present invention, some or all of the primary amine moieties canremain unmodified subject to the restrictions further described hereinbelow. These unmodified primary amine moieties by virtue of theirposition in the backbone chain remain “terminal” units. Likewise, when aprimary amine moiety, located at the end of the main polyamine backbonehaving the structure—NH₂is modified according to the present invention, it is thereafter definedas a Z “terminal” unit, or simply a Z unit. This unit can remainunmodified subject to the restrictions further described herein below.

In a similar manner, secondary amine nitrogens comprising the backboneor branching chain once modified are defined as W “backbone” units. Forexample, when a secondary amine moiety, the major constituent of thebackbones and branching chains of the present invention, having thestructure

is modified according to the present invention, it is thereafter definedas a W “backbone” unit, or simply a W unit. However, for the purposes ofthe present invention, some or all of the secondary amine moieties canremain unmodified. These unmodified secondary amine moieties by virtueof their position in the backbone chain remain “backbone” units.

In a further similar manner, tertiary amine nitrogens comprising thebackbone or branching chain once modified are further referred to as Y“branching” units. For example, when a tertiary amine moiety, which is achain branch point of either the polyamine backbone or other branchingchains or rings, having the structure

is modified according to the present invention, it is thereafter definedas a Y “branching” unit, or simply a Y unit. However, for the purposesof the present invention, some or all or the tertiary amine moieties canremain unmodified. These unmodified tertiary amine moieties by virtue oftheir position in the backbone chain remain “branching” units. The Runits associated with the V, W and Y unit nitrogens which serve toconnect the polyamine nitrogens, are described herein below.

The final modified structure of the polyamines of the present inventioncan be therefore represented by the general formulaV_((n+1))W_(m)Y _(n)Zfor linear amino-functional polymer and by the general formulaV_((n−k+1))W_(m)Y_(n)Y′_(k)Zfor cyclic amino-functional polymer. For the case of polyaminescomprising rings, a Y′ unit of the formula

serves as a branch point for a backbone or branch ring. For every Y′unit there is a Y unit having the formula

that will form the connection point of the ring to the main polymerchain or branch. In the unique case where the backbone is a completering, the polyamine backbone has the formula

therefore comprising no Z terminal unit and having the formulaV_(n−k)W_(m)Y_(n)Y′_(k)wherein k is the number of ring forming branching units. Preferably thepolyamine backbones of the present invention comprise no rings.

In the case of non-cyclic polyamines, the ratio of the index n to theindex m relates to the relative degree of branching. A fullynon-branched linear modified polyamine according to the presentinvention has the formulaVW_(m)Zthat is, n is equal to 0. The greater the value of n (the lower theratio of m to n), the greater the degree of branching in the molecule.Typically the value for m ranges from a minimum value of 2 to 700,preferably 4 to 400, however larger values of m, especially when thevalue of the index n is very low or nearly 0, are also preferred.

Each polyamine nitrogen whether primary, secondary or tertiary, oncemodified according to the present invention, is further defined as beinga member of one of three general classes; simple substituted,quaternized or oxidized. Those polyamine nitrogen units not modified areclassed into V, W, Y, Y′ or Z units depending on whether they areprimary, secondary or tertiary nitrogens. That is unmodified primaryamine nitrogens are V or Z units, unmodified secondary amine nitrogensare W units or Y′ units and unmodified tertiary amine nitrogens are Yunits for the purposes of the present invention.

Modified primary amine moieties are defined as V “terminal” units havingone of three forms:

-   -   a) simple substituted units having the structure:    -   b) quaternized units having the structure:        wherein X is a suitable counter ion providing charge balance;        and    -   c) oxidized units having the structure:

Modified secondary amine moieties are defined as W “backbone” unitshaving one of three forms:

-   -   a) simple substituted units having the structure:    -   b) quaternized units having the structure:        wherein X is a suitable counter ion providing charge balance;        and    -   c) oxidized units having the structure:

Other modified secondary amine moieties are defined as Y′ units havingone of three forms:

-   -   a) simple substituted units having the structure:    -   b) quaternized units having the structure:        wherein X is a suitable counter ion providing charge balance;        and    -   c) oxidized units having the structure:

Modified tertiary amine moieties are defined as Y “branching” unitshaving one of three forms:

-   -   a) unmodified units having the structure:    -   b) quaternized units having the structure:        wherein X is a suitable counter ion providing charge balance;        and    -   c) oxidized units having the structure:

Certain modified primary amine moieties are defined as Z “terminal”units having one of three forms:

-   -   a) simple substituted units having the structure:    -   b) quaternized units having the structure:        wherein X is a suitable counter ion providing charge balance;        and    -   c) oxidized units having the structure:

When any position on a nitrogen is unsubstituted of unmodified, it isunderstood that hydrogen will substitute for R′. For example, a primaryamine unit comprising one R′ unit in the form of a hydroxyethyl moietyis a V terminal unit having the formula (HOCH₂CH₂)HN—.

For the purposes of the present invention there are two types of chainterminating units, the V and Z units. The Z “terminal” unit derives froma terminal primary amino moiety of the structure —NH₂. Non-cyclicpolyamine backbones according to the present invention comprise only oneZ unit whereas cyclic polyamines can comprise no Z units. The Z“terminal” unit can be substituted with any of the R′ units describedfurther herein below, except when the Z unit is modified to form anN-oxide. In the case where the Z unit nitrogen is oxidized to anN-oxide, the nitrogen must be modified and therefore R′ cannot be ahydrogen.

The polyamines of the present invention comprise backbone R “linking”units that serve to connect the nitrogen atoms of the backbone. R unitscomprise units that for the purposes of the present invention arereferred to as “hydrocarbyl R” units and “oxy R” units. The“hydrocarbyl” R units are C₂-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₃-C₁₂hydroxyalkylene wherein the hydroxyl moiety may take any position on theR unit chain except the carbon atoms directly connected to the polyaminebackbone nitrogens; C₄-C₁₂ dihydroxyalkylene wherein the hydroxylmoieties may occupy any two of the carbon atoms of the R unit chainexcept those carbon atoms directly connected to the polyamine backbonenitrogens; C₈-C₁₂ dialkylarylene which for the purpose of the presentinvention are arylene moieties having two alkyl substituent groups aspart of the linking chain. For example, a dialkylarylene unit has theformula

although the unit need not be 1,4-substituted, but can also be 1,2 or1,3 substituted C₂-C₁₂ alkylene, preferably ethylene, 1,2-propylene, andmixtures thereof, more preferably ethylene. The “oxy” R units comprise-(R¹O)_(x)R⁵(OR¹)_(x)-,—CH₂CH(OR²)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH(OR²)CH₂)_(w)—, —CH₂CH(OR²)CH₂—,—(R¹O)_(x)R¹-, and mixtures thereof. Preferred R units are selected fromthe group consisting of C₂-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂dihydroxyalkylene, C₈-C₁₂ dialkylarylene, -(R¹O)_(x)R¹-,—CH₂CH(OR²)CH₂—, —(CH₂CH(OH)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH—(OH)CH₂)_(w)—,-(R¹O)_(x)R⁵(OR¹)_(x)-, more preferred R units are C₂-C₁₂ alkylene,C₃-C₁₂ hydroxy-alkylene, C₄-C₁₂ dihydroxyalkylene, -(R¹O)_(x)R¹-,-(R¹O)_(x)R⁵(OR¹)_(x)-,—(CH₂CH(OH)CH₂O)_(z)(R¹O)_(y)R¹(OCH₂CH—(OH)CH₂)_(w)—, and mixturesthereof, even more preferred R units are C₂-C₁₂ alkylene, C₃hydroxyalkylene, and mixtures thereof, most preferred are C₂-C₆alkylene. The most preferred backbones of the present invention compriseat least 50% R units that are ethylene.

-   -   R¹ units are C₂-C₆ alkylene, and mixtures thereof, preferably        ethylene.    -   R² is hydrogen, and -(R¹O)_(x)B, preferably hydrogen.    -   R³ is C₁-C₁₈ alkyl, C₇-C₁₂ arylalkylene, C₇-C₁₂ alkyl        substituted aryl, C₆-C₁₂ aryl, and mixtures thereof, preferably        C₁-C₁₂ alkyl, C₇-C₁₂ arylalkylene, more preferably C₁-C₁₂ alkyl,        most preferably methyl. R³ units serve as part of R′ units        described herein below.    -   R⁴ is C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₈-C₁₂ arylalkylene,        C₆-C₁₀ arylene, preferably C₁-C₁₀ alkylene, C₉-C₁₂ arylalkylene,        more preferably C₂-C₈ alkylene, most preferably ethylene or        butylene.    -   R⁵ is C₁-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂        dihydroxyalkylene, C₈-C₁₂ dialkylarylene, —C(O)—,        —C(O)NHR⁶NHC(O)—, —C(O)(R⁴)_(r)C(O)—, -R¹(OR¹)-,        —CH₂CH(OH)CH₂O(R¹O)_(y)R¹OCH₂CH(OH)CH₂—, —C(O)(R⁴)_(r)C(O)—,        —CH₂CH(OH)CH₂—, R⁵ is preferably ethylene, —C(O)—,        —C(O)NHR⁶NHC(O)—, -R¹(OR¹)-, —CH₂CH(OH)CH₂—,        —CH₂CH(OH)CH₂O(R¹O)_(y)R¹OCH₂CH—(OH)CH₂—, more preferably        —CH₂CH(OH)CH₂—.    -   R⁶ is C₂-C₁₂ alkylene or C₆-C₁₂ arylene.

The preferred “oxy” R units are further defined in terms of the R¹, R²,and R⁵ units. Preferred “oxy” k units comprise the preferred R¹, R², andR⁵ units. The preferred cotton soil release agents of the presentinvention comprise at least 50% R¹ units that are ethylene. PreferredR¹, R², and R⁵ units are combined with the “oxy” R units to yield thepreferred “oxy” R units in the following manner.

-   -   i) Substituting more preferred R⁵ into        —(CH₂CH₂O)_(x)R⁵(OCH₂CH₂)_(x)— yields        —(CH₂CH₂O)_(x)CH₂CHOHCH₂(OCH₂CH₂)_(x)—.    -   ii) Substituting preferred R¹ and R² into        —(CH₂CH(OR²)CH₂O)_(z)-(R¹O) _(y)R¹O(CH₂CH(OR²)CH₂)_(w)— yields        —(CH₂CH(OH)CH₂O)_(z)—(CH₂CH₂O)_(y)CH₂CH₂O(CH₂CH(OH)CH₂)_(w)—.    -   iii) Substituting preferred R² into —CH₂CH(OR²)CH₂— yields        —CH₂CH(OH)CH₂—.

R′ units are selected from the group consisting of hydrogen, C₁-C₂₂alkyl, C₃-C₂₂ alkenyl, C₇-C₂₂ arylalkyl, C₂-C₂₂ hydroxyalkyl,—(CH₂)_(p)CO₂M, —(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M, —(CH₂)_(p)PO₃M,-(R¹O)_(m)B, —C(O)R³, preferably hydrogen, C₂-C₂₂ hydroxyalkylene,benzyl, C₁-C₂₂ alkylene, -(R¹O)_(m)B, —C(O)R³, —(CH₂)_(p)CO₂M,—(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M, more preferably C₁-C₂₂ alkylene,-(R¹O)_(x)B, —C(O)R³, —(CH₂)_(p)CO₂M, —(CH₂)_(q)SO₃M, —CH(CH₂CO₂M)CO₂M,most preferably C₁-C₂₂ alkylene, -(R¹O)_(x)B, and —C(O)R³. When nomodification or substitution is made on a nitrogen then hydrogen atomwill remain as the moiety representing R′. A most preferred R′ unit is(R¹O)_(x)B.

R′ units do not comprise hydrogen atom when the V, W or Z units areoxidized, that is the nitrogens are N-oxides. For example, the backbonechain or branching chains do not comprise units of the followingstructure:

Additionally, R′ units do not comprise carbonyl moieties directly bondedto a nitrogen atom when the V, W or Z units are oxidized, that is, thenitrogens are N-oxides. According to the present invention, the R′ unit—C(O)R³ moiety is not bonded to an N-oxide modified nitrogen, that is,there are no N-oxide amides having the structure

or combinations thereof.

B is hydrogen, C₁-C₆ alkyl, —(CH₂)_(q)SO₃M, —(CH₂)_(p)CO₂M,—(CH₂)_(q)—(CHSO₃M)CH₂SO₃M, —(CH₂)_(q)(CHSO₂M)CH₂SO₃M, —(CH₂)_(p)PO₃M,—PO₃M, preferably hydrogen, —(CH₂)_(q)SO₃M, —(CH₂)_(q)(CHSO₃M)CH₂SO₃M,—(CH₂)_(q)—(CHSO₂M)CH₂SO₃M, more preferably hydrogen or —(CH₂)_(q)SO₃M.

M is hydrogen or a water soluble cation in sufficient amount to satisfycharge balance. For example, a sodium cation equally satisfies—(CH₂)_(p)CO₂M, and —(CH₂)_(q)SO₃M, thereby resulting in—(CH₂)_(p)CO₂Na, and —(CH₂)_(q)SO₃Na moieties. More than one monovalentcation, (sodium, potassium, etc.) can be combined to satisfy therequired chemical charge balance. However, more than one anionic groupmay be charge balanced by a divalent cation, or more than onemono-valent cation may be necessary to satisfy the charge requirementsof a poly-anionic radical. For example, a —(CH₂)_(p)PO₃M moietysubstituted with sodium atoms has the formula —(CH₂)_(p)PO₃Na₃. Divalentcations such as calcium (Ca²⁺) or magnesium (Mg²⁺) may be substitutedfor or combined with other suitable mono-valent water soluble cations.Preferred cations are sodium and potassium, more preferred is sodium.

X is a water soluble anion such as chlorine (Cl⁻), bromine (Br⁻) andiodine (I⁻) or X can be any negatively charged radical such as sulfate(SO₄ ²—) and methosulfate (CH₃ SO₃—).

The formula indices have the following values: p has the value from 1 to6, q has the value from 0 to 6; r has the value 0 or 1; w has the value0 or 1, x has the value from 1 to 100; y has the value from 0 to 100; zhas the value 0 or 1; m has the value from 2 to 700, preferably from 4to 400, n has the value from 0 to 350, preferably from 0 to 200; m+n hasthe value of at least 5.

Preferably x has a value lying in the range of from 1 to 20, preferablyfrom 1 to 10.

The preferred amino-functional polymers of the present inventioncomprise polyamine backbones wherein less than 50% of the R groupscomprise “oxy” R units, preferably less than 20%, more preferably lessthan 5%, most preferably the R units comprise no “oxy” R units.

The most preferred amino-functional polymers which comprise no “oxy” Runits comprise polyamine backbones wherein less than 50% of the R groupscomprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene,and 1,3-propylene comprise 3 or less carbon atoms and are the preferred“hydrocarbyl” R units. That is when backbone R units are C₂-C₁₂alkylene, preferred is C₂-C₃ alkylene, most preferred is ethylene.

The amino-functional polymers of the present invention comprise modifiedhomogeneous and non-homogeneous polyamine backbones, wherein 100% orless of the —NH units are modified. For the purpose of the presentinvention the term “homogeneous polyamine backbone” is defined as apolyamine backbone having R units that are the same (i.e., allethylene). However, this sameness definition does not exclude polyaminesthat comprise other extraneous units comprising the polymer backbonewhich are present due to an artifact of the chosen method of chemicalsynthesis. For example, it is known to those skilled in the art thatethanolamine may be used as an “initiator” in the synthesis ofpolyethyleneimines, therefore a sample of polyethyleneimine thatcomprises one hydroxyethyl moiety resulting from the polymerization“initiator” would be considered to comprise a homogeneous polyaminebackbone for the purposes of the present invention. A polyamine backbonecomprising all ethylene R units wherein no branching Y units are presentis a homogeneous backbone. A polyamine backbone comprising all ethyleneR units is a homogeneous backbone regardless of the degree of branchingor the number of cyclic branches present.

For the purposes of the present invention the term “non-homogeneouspolymer backbone” refers to polyamine backbones that are a composite ofvarious R unit lengths and R unit types. For example, a non-homogeneousbackbone comprises R units that are a mixture of ethylene and1,2-propylene units. For the purposes of the present invention a mixtureof “hydrocarbyl” and “oxy” R units is not necessary to provide anon-homogeneous backbone.

Preferred amino-functional polymers of the present invention comprisehomogeneous polyamine backbones that are totally or partiallysubstituted by polyethyleneoxy moieties, totally or partiallyquaternized amines, nitrogens totally or partially oxidized to N-oxides,and mixtures thereof. However, not all backbone amine nitrogens must bemodified in the same manner, the choice of modification being left tothe specific needs of the formulator.

The degree of ethoxylation is also determined by the specificrequirements of the formulator.

The preferred polyamines that comprise the backbone of the compounds ofthe present invention are generally polyalkyleneimines (PAI's),preferably polyethyleneimines (PEI's), or PEI's connected by moietieshaving longer R units than the parent PAI's or PEI's.

Preferred amine polymer backbones comprise R units that are C₂ alkylene(ethylene) units, also known as polyethylenimines (PEI's). PreferredPEI's have at least moderate branching, that is the ratio of m to n isless than 4:1, however PEI's having a ratio of m to n of 2:1 are mostpreferred. Preferred backbones, prior to modification have the generalformula:

wherein R′, m and n are the same as defined herein above. PreferredPEI's will have a molecular weight greater than 200 daltons.

The relative proportions of primary, secondary and tertiary amine unitsin the polyamine backbone, especially in the case of PEI's, will vary,depending on the manner of preparation. Each hydrogen atom attached toeach nitrogen atom of the polyamine backbone chain represents apotential site for subsequent substitution, quaternization or oxidation.

These polyamines can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods for preparing these polyaminebackbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al.,issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16,1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and U.S.Pat. No. 2,553,696, Wilson, issued May 21, 1951; all herein incorporatedby reference.

The present invention allows the formulator to have a portion of thesecondary amine nitrogens ethoxylated while having other secondary aminenitrogens oxidized to N-oxides. This also applies to the primary aminenitrogens, in that the formulator may choose to modify all or a portionof the primary amine nitrogens with one or more substituents prior tooxidation or quaternization. Any possible combination of R′ groups canbe substituted on the primary and secondary amine nitrogens, except forthe restrictions described herein above.

Commercially available amino-functional polymer suitable for use hereinare poly(ethyleneimine) with a MW 1200, hydroxyethylatedpoly(ethyleneimine) from Polysciences, with a MW 2000, and 80%hydroxyethylated poly(ethyleneimine) from Aldrich. Still other suitableamino-functional polymer are oligoamine of low molecular weight. Mostparticularly preferred for use herein are oligoamines selected from1,4-Bis(3-aminopropyl) piperazine,N,N′-Bis(3-aminopropyl)1,3-propanediamine, and mixtures therof.

A typical amount of amino-functional polymer to be employed in thecomposition of the invention is preferably up to 90% by weight,preferably from 0.01% to 50% active by weight, more preferably from 0.1%to 20% by weight and most preferably from 0.5% to 15% by weight of thecomposition.

Crystal Growth Inhibitor Component

The compositions of the present invention can further contain a crystalgrowth inhibitor component, preferably an organodiphosphonic acidcomponent, and/or organo monophosphonic acid, incorporated preferably ata level of from 0.01% to 5%, more preferably from 0.1% to 2% by weightof the compositions.

By organo diphosphonic acid it is meant herein an organo diphosphonicacid which does not contain nitrogen as part of its chemical structure.This definition therefore excludes the organo aminophosphonates, whichhowever may be included in compositions of the invention as heavy metalion sequestrant components.

The organo diphosphonic acid is preferably a C₁-C₄ diphosphonic acid,more preferably a C₂ diphosphonic acid, such as ethylene diphosphonicacid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP)and may be present in partially or fully ionized form, particularly as asalt or complex.

Still useful herein as crystal growth inhibitor are the organicmonophosphonic acid Organo monophosphonic acid or one of its salts orcomplexes is also suitable for use herein as a CGI.

By organo monophosphonic acid it is meant herein an organomonophosphonic acid which does not contain nitrogen as part of itschemical structure. This definition therefore excludes the organoaminophosphonates, which however may be included in compositions of theinvention as heavy metal ion sequestrants.

The organo monophosphonic acid component may be present in its acid formor in the form of one of its salts or complexes with a suitable countercation. Preferably any salts/complexes are water soluble, with thealkali metal and alkaline earth metal salts/complexes being especiallypreferred.

A prefered organo monophosphonic acid is2-phosphonobutane-1,2,4-tricarboxylic acid commercially available fromBayer under the tradename of Bayhibit.

Still other components may be suitable for use in the present inventionare as follows:

Soil Release Agent

Soil Release agents are desirably used in fabric care compositions ofthe present invention. Any polymeric soil release agent known to thoseskilled in the art can optionally be employed in the compositions ofthis invention. Polymeric soil release agents are characterized byhaving both hydrophilic segments, to hydrophilize the surface ofhydrophobic fibers, such as polyester and nylon, and hydrophobicsegments, to deposit upon hydrophobic fibers and remain adhered theretothrough completion of washing and rinsing cycles and, thus, serve as ananchor for the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

The following, all included herein by reference, describe soil releasepolymers suitable for use in the present invention. U.S. Pat. No.3,959,230 Hays, issued May 25, 1976; U.S. Pat. No. 3,893,929 Basadur,issued Jul. 8, 1975; U.S. Pat. No. 4,000,093, Nicol, et al., issued Dec.28, 1976; U.S. Pat. No. 4,702,857 Gosselink, issued Oct. 27, 1987; U.S.Pat. No. 4,968,451, Scheibel et al., issued November 6; U.S. Pat. No.4,702,857, Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,711,730,Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580,Gosselink, issued Jan. 26, 1988; U.S. Pat. No. 4,877,896, Maldonado etal., issued Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 5,415,807 Gosselink et al., issuedMay 16, 1995; European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824, Violland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681, Ruppert et al.;U.S. Pat. No. 4,240,918; U.S. Pat. No. 4,787,989; U.S. Pat. No.4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A toBASF (1991); and DE 2,335,044 to Unilever N. V., 1974 all incorporatedherein by reference.

Commercially available soil release agents include the METOLOSE SM100,METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K. K., SOKALANtype of material, e.g., SOKALAN HP-22, available from BASF (Germany),ZELCON 5126 (from Dupont) and MILEASE T (from ICI).

When the composition is formulated as a softening composition, it willalso comprises a fabric softening compound.

Fabric Softening Compound

Typical levels of incorporation of the softening compound in thecomposition are of from 1% to 80% by weight, preferably from 5% to 75%,more preferably from 15% to 70%, and even more preferably from 19% to65%, by weight of the composition.

Typical of the cationic softening components are the quaternary ammoniumcompounds or amine precursors thereof as defined hereinafter.

A)-Quaternary Ammonium Fabric Softening Active Compound

(1) Preferred quaternary ammonium fabric softening active compound havethe formula

or the formula:

wherein Q is a carbonyl unit having the formula:

each R unit is independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,and mixtures thereof, preferably methyl or hydroxy alkyl; each R¹ unitis independently linear or branched C₁₁-C₂₂ alkyl, linear or branchedC₁₁-C₂₂ alkenyl, and mixtures thereof, R² is hydrogen, C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, and mixtures thereof, X is an anion which iscompatible with fabric softener actives and adjunct ingredients; theindex m is from 1 to 4, preferably 2; the index n is from 1 to 4,preferably 2.

An example of a preferred fabric softener active is a mixture ofquaternized amines having the formula:

wherein R is preferably methyl; R¹ is a linear or branched alkyl oralkenyl chain comprising at least 11 atoms, preferably at least 15atoms. In the above fabric softener example, the unit —O₂CR¹ representsa fatty acyl unit which is typically derived from a triglyceride source.The triglyceride source is preferably derived from tallow, partiallyhydrogenated tallow, lard, partially hydrogenated lard, vegetable oilsand/or partially hydrogenated vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talloil, rice bran oil, etc. and mixtures of these oils.

The preferred fabric softening actives of the present invention are theDiester and/or Diamide Quaternary Ammonium (DEQA) compounds, thediesters and diamides having the formula:

wherein R, R¹, X, and n are the same as defined herein above forformulas (1) and (2), and Q has the formula:

These preferred fabric softening actives are formed from the reaction ofan amine with a fatty acyl unit to form an amine intermediate having theformula:

wherein R is preferably methyl, Q and R¹ are as defined herein before;followed by quaternization to the final softener active.

Non-limiting examples of preferred amines which are used to form theDEQA fabric softening actives according to the present invention includemethyl bis(2-hydroxyethyl) amine having the formula:

methyl bis(2-hydroxypropyl)amine having the formula:

methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:

methyl bis(2-aminoethyl)amine having the formula:

triethanol amine having the formula:

di(2-aminoethyl) ethanolamine having the formula:

The counterion, X(⁻) above, can be any softener-compatible anion,preferably the anion of a strong acid, for example, chloride, bromide,methylsulfate, ethylsulfate, sulfate, nitrate and the like, morepreferably chloride or methyl sulfate. The anion can also, but lesspreferably, carry a double charge in which case X(⁻) represents half agroup.

Tallow and canola oil are convenient and inexpensive sources of fattyacyl units which are suitable for use in the present invention as R¹units. The following are non-limiting examples of quaternary ammoniumcompounds suitable for use in the compositions of the present invention.The term “tallowyl” as used herein below indicates the R¹ unit isderived from a tallow triglyceride source and is a mixture of fattyalkyl or alkenyl units. Likewise, the use of the term canolyl refers toa mixture of fatty alkyl or alkenyl units derived from canola oil.

In the following table are described non-limiting examples of suitablefabric softener according to the above formula. In this list, the term“oxy” defines a

unit, whereas the term “oxo” defines a —O— unit. TABLE II FabricSoftener Actives N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl,N-(2-hydroxyethyl) ammonium chloride;N,N-di(canolyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl) ammoniumchloride; N,N-di(tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammoniumchloride; N,N-di(canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chlorideN,N,N-tri(tallowyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;N,N,N-tri(canolyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;N-(tallowyloxy-2-oxo-ethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;N-(canolyloxy-2-oxo-ethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;1,2-di(tallowyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride; and1,2-di(canolyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride; andmixtures of the above actives.

Other examples of quaternay ammoniun softening compounds aremethylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate andmethylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammoniummethylsulfate; these materials are available from Witco Chemical Companyunder the trade names Varisoft® 222 and Varisoft® 110, respectively.

Particularly preferred is N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl,N-(2-hydroxyethyl) ammonium chloride, where the tallow chains are atleast partially unsaturated.

The level of unsaturation contained within the tallow, canola, or otherfatty acyl unit chain can be measured by the Iodine Value (IV) of thecorresponding fatty acid, which in the present case should preferably bein the range of from 5 to 100 with two categories of compounds beingdistinguished, having a IV below or above 25.

Indeed, for compounds having the formula:

derived from tallow fatty acids, when the Iodine Value is from 5 to 25,preferably 15 to 20, it has been found that a cis/trans isomer weightratio greater than about 30/70, preferably greater than about 50/50 andmore preferably greater than about 70/30 provides optimalconcentrability.

For compounds of this type made from tallow fatty acids having a IodineValue of above 25, the ratio of cis to trans isomers has been found tobe less critical unless very high concentrations are needed.

Other suitable examples of fabric softener actives are derived fromfatty acyl groups wherein the terms “tallowyl” and canolyl” in the aboveexamples are replaced by the terms “cocoyl, palmyl, lauryl, oleyl,ricinoleyl, stearyl, palmityl,” which correspond to the triglyceridesource from which the fatty acyl units are derived. These alternativefatty acyl sources can comprise either fully saturated, or preferably atleast partly unsaturated chains.

As described herein before, R units are preferably methyl, however,suitable fabric softener actives are described by replacing the term“methyl” in the above examples in Table II with the units “ethyl,ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl.

The counter ion, X, in the examples of Table II can be suitably replacedby bromide, methylsulfate, formate, sulfate, nitrate, and mixturesthereof. In fact, the anion, X, is merely present as a counterion of thepositively charged quaternary ammonium compounds. The scope of thisinvention is not considered limited to any particular anion.

For the preceding ester fabric softening agents, the pH of thecompositions herein is an important parameter of the present invention.Indeed, it influences the stability of the quaternary ammonium or amineprecursors compounds, especially in prolonged storage conditions.

The pH, as defined in the present context, is measured in the neatcompositions at 20 ° C. While these compositions are operable at pH ofless than about 6.0, for optimum hydrolytic stability of thesecompositions, the neat pH, measured in the above-mentioned conditions,must preferably be in the range of from about 2.0 to about 5, preferablyin the range of 2.5 to 4.5, preferably about 2.5 to about 3.5. The pH ofthese compositions herein can be regulated by the addition of a Bronstedacid.

Examples of suitable acids include the inorganic mineral acids,carboxylic acids, in particular the low molecular weight (C₁-C₅)carboxylic acids, and alkylsulfonic acids. Suitable inorganic acidsinclude HCl, H₂SO₄, HNO₃ and H₃PO₄. Suitable organic acids includeformic, acetic, citric, methylsulfonic and ethylsulfonic acid. Preferredacids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid,and benzoic acids.

As used herein, when the diester is specified, it will include themonoester that is normally present in manufacture. For softening, underno/low detergent carry-over laundry conditions the percentage ofmonoester should be as low as possible, preferably no more than about2.5%. However, under high detergent carry-over conditions, somemonoester is preferred. The overall ratios of diester to monoester arefrom about 100:1 to about 2:1, preferably from about 50:1 to about 5:1,more preferably from about 13:1 to about 8:1. Under high detergentcarry-over conditions, the di/monoester ratio is preferably about 11:1.The level of monoester present can be controlled in the manufacturing ofthe softener compound.

Mixtures of actives of formula (1) and (2) may also be prepared.

2)-Still other suitable quaternary ammonium fabric softening compoundsfor use herein are cationic nitrogenous salts having two or more longchain acyclic aliphatic C₈-C₂₂ hydrocarbon groups or one said group andan arylalkyl group which can be used either alone or as part of amixture are selected from the group consisting of:

-   -   (i) acyclic quaternary ammonium salts having the formula:        wherein R⁴ is an acyclic aliphatic C₈-C₂₂ hydrocarbon group, R⁵        is a C₁-C₄ saturated alkyl or hydroxyalkyl group, R⁸ is selected        from the group consisting of R⁴ and R⁵ groups, and A- is an        anion defined as above;    -   (ii) diamino alkoxylated quaternary ammonium salts having the        formula:        wherein n is equal to 1 to about 5, and R¹, R², R⁵ and A- are as        defined above;    -   (iii) mixtures thereof.

Examples of the above class cationic nitrogenous salts are thewell-known dialkyldi methylammonium salts such asditallowdimethylammonium chloride, ditallowdimethylammoniummethylsulfate, di(hydrogenatedtallow)dimethylammonium chloride,distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.Di(hydrogenatedtallow)di methylammonium chloride andditallowdimethylammonium chloride are preferred. Examples ofcommercially available dialkyldimethyl ammonium salts usable in thepresent invention are di(hydrogenatedtallow)dimethylammonium chloride(trade name Adogen® 442), ditallowdimethylammonium chloride (trade nameAdogen® 470, Praepagen® 3445), distearyl dimethylammonium chloride(trade name Arosurf® TA-100), all available from Witco Chemical Company.Dibehenyldimethylammonium chloride is sold under the trade name KemamineQ-2802C by Humko Chemical Division of Witco Chemical Corporation.

Dimethylstearylbenzyl ammonium chloride is sold under the trade namesVarisoft® SDC by Witco Chemical Company and Ammonyx® 490 by OnyxChemical Company.

B)-Amine Fabric Softening Active Compound

Suitable amine fabric softening compounds for use herein, which may bein amine form or cationic form are selected from:

(i)- Reaction products of higher fatty acids with a polyamine selectedfrom the group consisting of hydroxyalkylalkylenediamines anddialkylenetriamines and mixtures thereof. These reaction products aremixtures of several compounds in view of the multi-functional structureof the polyamines.

The preferred Component (i) is a nitrogenous compound selected from thegroup consisting of the reaction product mixtures or some selectedcomponents of the mixtures. One preferred component (i) is a compoundselected from the group consisting of substituted imidazoline compoundshaving the formula:

wherein R⁷ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group and R⁸ is adivalent C₁-C₃ alkylene group.

Component (i) materials are commercially available as: Mazamide® 6, soldby Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals;stearic hydroxyethyl imidazoline sold under the trade names of Alkazine®ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals,Inc.; N,N″-ditallowalkoyldiethylenetriamine;1-tallowamidoethyl-2-tallowimidazoline (wherein in the precedingstructure R¹ is an aliphatic C ₁₅-C₁₇ hydrocarbon group and R⁸ is adivalent ethylene group).

Certain of the Components (i) can also be first dispersed in a Bronstedacid dispersing aid having a pKa value of not greater than about 4;provided that the pH of the final composition is not greater than about6. Some preferred dispersing aids are hydrochloric acid, phosphoricacid, or methylsulfonic acid.

Both N,N″-ditallowalkoyldiethylenetriamine and1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of tallowfatty acids and diethylenetriamine, and are precursors of the cationicfabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazoliniummethylsulfate (see “Cationic Surface Active Agents as Fabric Softeners,”R. R. Egan, Journal of the American Oil Chemicals' Society, January1978, pages 118-121). N,N″-ditallow alkoyldiethylenetriamine and1-tallowamidoethyl-2-tallowimidazoline can be obtained from WitcoChemical Company as experimental chemicals.Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold byWitco Chemical Company under the tradename Varisoft® 475.

(ii)-softener having the formula:

wherein each R² is a C₁₋₆ alkylene group, preferably an ethylene group;and G is an oxygen atom or an —NR— group; and each R, R¹, R² and R⁵ havethe definitions given above and A- has the definitions given above forX⁻.

An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazoliniumchloride wherein R¹ is an acyclic aliphatic C₁₅-C₁₇ hydrocarbon group,R² is an ethylene group, G is a NH group, R⁵ is a methyl group and A- isa chloride anion.

(iii)- softener having the formula:

wherein R, R¹, R², and A- are defined as above.

An example of Compound (iii) is the compound having the formula:

wherein R¹ is derived from oleic acid.

Additional fabric softening agents useful herein are described in U.S.Pat. No. 4,661,269, issued Apr. 28, 1987, in the names of Toan Trinh,Errol H. Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat.No. 4,439,335, Burns, issued Mar. 27, 1984; and in U.S. Pat. Nos.:3,861,870, Edwards and Diehl; 4,308,151, Cambre; 3,886,075, Bernardino;4,233,164, Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema and Rieke;4,237,016, Rudkin, Clint, and Young; and European Patent Applicationpublication No. 472,178, by Yamamura et al., all of said documents beingincorporated herein by reference.

Of course, the term “softening active” can also encompass mixedsoftening active agents. Preferred among the classes of softenercompounds disclosed herein before are the diester or diamido quaternaryammonium fabric softening active compound (DEQA).

Fully formulated fabric softening compositions may contain, in additionto the hereinbefore described components, one or more of the followingingredients.

Optional Ingredients

(A)Liquid carrier

Another optional, but preferred, ingredient is a liquid carrier. Theliquid carrier employed in the instant compositions is preferably atleast primarily water due to its low cost, relative availability,safety, and environmental compatibility. The level of water in theliquid carrier is preferably at least about 50%, most preferably atleast about 60%, by weight of the carrier. Mixtures of water and lowmolecular weight, e.g., <about 200, organic solvent, e.g., loweralcohols such as ethanol, propanol, isopropanol or butanol are useful asthe carrier liquid. Low molecular weight alcohols include monohydric,dihydric (glycol, etc.) trihydric (glycerol, etc.), and higherpolyhydric (polyols) alcohols.

(B)-Additional Solvents

The compositions of the present invention may comprise one or moresolvents which provide increased ease of formulation. These ease offormulation solvents are all disclosed in WO 97/03169. This isparticularly the case when formulating liquid, clear fabric softeningcompositions. When employed, the ease of formulation solvent systempreferably comprises less than about 40%, preferably from about 10% toabout 35%, more preferably from about 12% to about 25%, and even morepreferably from about 14% to about 20%, by weight of the composition.The ease of formulation solvent is selected to minimize solvent odorimpact in the composition and to provide a low viscosity to the finalcomposition. For example, isopropyl alcohol is not very effective andhas a strong odor. n-Propyl alcohol is more effective, but also has adistinct odor. Several butyl alcohols also have odors but can be usedfor effective clarity/stability, especially when used as part of a easeof formulation solvent system to minimize their odor. The alcohols arealso selected for optimum low temperature stability, that is they areable to form compositions that are liquid with acceptable lowviscosities and translucent, preferably clear, down to about 40° F.(about 4.4° C.) and are able to recover after storage down to about 20°F. (about minus 6.7° C.).

The suitability of any ease of formulation solvent for the formulationof the liquid, concentrated, preferably clear, fabric softenercompositions herein with the requisite stability is surprisinglyselective. Suitable solvents can be selected based upon theiroctanol/water partition coefficient (P) as defined in WO 97/03169.

The ease of formulation solvents herein are selected from those having aClogP of from about 0.15 to about 0.64, preferably from about 0.25 toabout 0.62, and more preferably from about 0.40 to about 0.60, said easeof formulation solvent preferably being at least somewhat asymmetric,and preferably having a melting, or solidification, point that allows itto be liquid at, or near room temperature. Solvents that have a lowmolecular weight and are biodegradable are also desirable for somepurposes. The more assymetric solvents appear to be very desirable,whereas the highly symmetrical solvents such as 1,7-heptanediol, or1,4-bis(hydroxymethyl) cyclohexane, which have a center of symmetry,appear to be unable to provide the essential clear compositions whenused alone, even though their ClogP values fall in the preferred range.

The most preferred ease of formulation solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active.

Operable ease of formulation solvents are disclosed and listed belowwhich have ClogP values which fall within the requisite range. Theseinclude mono-ols, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trimethylpentanediol isomers, ethylmethylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols. Particularly preferred ease of formulation solventsinclude hexanediols such as 1,2-Hexanediol and 2-Ethyl-1,3-hexanedioland pentanediols such as 2,2,4-Trimethyl-1,3-pentanediol.

(C) Dispersibility Aids

Relatively concentrated compositions containing both saturated andunsaturated diester quaternary ammonium compounds can be prepared thatare stable without the addition of concentration aids. However, thecompositions of the present invention may require organic and/orinorganic concentration aids to go to even higher concentrations and/orto meet higher stability standards depending on the other ingredients.These concentration aids which typically can be viscosity modifiers maybe needed, or preferred, for ensuring stability under extreme conditionswhen particular softener active levels are used. The surfactantconcentration aids are typically selected from the group consisting of(1) single long chain alkyl cationic surfactants; (2) nonionicsurfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereofThese aids are described in WO 94/20597, specifically on page 14, line12 to page 20, line 12, which is herein incorporated by reference.

When said dispersibility aids are present, the total level is from 2% to25%, preferably from 3% to 17%, more preferably from 4% to 15%, and evenmore preferably from 5% to 13% by weight of the composition. Thesematerials can either be added as part of the active softener rawmaterial, (I), e.g., the mono-long chain alkyl cationic surfactantand/or the fatty acid which are reactants used to form the biodegradablefabric softener active as discussed hereinbefore, or added as a separatecomponent. The total level of dispersibility aid includes any amountthat may be present as part of component (I).

Inorganic viscosity/dispersibility control agents which can also actlike or augment the effect of the surfactant concentration aids, includewater-soluble, ionizable salts which can also optionally be incorporatedinto the compositions of the present invention. A wide variety ofionizable salts can be used. Examples of suitable salts are the halidesof the Group IA and IIA metals of the Periodic Table of the Elements,e.g., calcium chloride, magnesium chloride, sodium chloride, potassiumbromide, and lithium chloride. The ionizable salts are particularlyuseful during the process of mixing the ingredients to make thecompositions herein, and later to obtain the desired viscosity. Theamount of ionizable salts used depends on the amount of activeingredients used in the compositions and can be adjusted according tothe desires of the formulator. Typical levels of salts used to controlthe composition viscosity are from about 20 to about 20,000 parts permillion (ppm), preferably from about 20 to about 11,000 ppm, by weightof the composition.

Alkylene polyammonium salts can be incorporated into the composition togive viscosity control in addition to or in place of the water-soluble,ionizable salts above. In addition, these agents can act as scavengers,forming ion pairs with anionic detergent carried over from the mainwash, in the rinse, and on the fabrics, and may improve softnessperformance. These agents may stabilize the viscosity over a broaderrange of temperature, especially at low temperatures, compared to theinorganic electrolytes.

Specific examples of alkylene polyammonium salts include 1-lysinemonohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.

(D)-Stabilizers

Stabilizers can be present in the compositions of the present invention.The term “stabilizer,” as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% toabout 2%, preferably from about 0.01% to about 0.2%, more preferablyfrom about 0.035% to about 0.1% for antioxidants, and more preferablyfrom about 0.01% to about 0.2% for reductive agents. These assure goododor stability under long term storage conditions for the compositionsand compounds stored in molten form. The use of antioxidants andreductive agent stabilizers is especially critical for low scentproducts (low perfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox-6; butylated hydroxytoluene, available from UOP ProcessDivision under the trade name Sustane® BHT; tertiary butylhydroquinone,Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols,Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylatedhydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chainesters (C₈-C₂₂) of gallic acid, e.g., dodecyl gallate; Irganox® 1010;Irganox® 1035; Irganox® B 1171; Irganox® 1425; Irganox® 3114; Irganox®3125; and mixtures thereof; preferably Irganox® 3125, Irganox® 1425,Irganox® 3114, and mixtures thereof; more preferably Irganox® 3125alone. The chemical names and CAS numbers for some of the abovestabilizers are listed in Table II below. TABLE II Chemical Name used inCode of Federal Antioxidant CAS No. Regulations Irganox ® 1010 6683-19-8 Tetrakis (methylene(3,5-di-tert-butyl-4hydroxyhydrocinnamate)) methane Irganox ® 1035 41484-35-9 Thiodiethylenebis(3,5-di-tert-butyl-4- hydroxyhydrocinnamate Irganox ® 1098 23128-74-7N,N′-Hexamethylene bis(3,5-di-tert-butyl-4- hydroxyhydrocinnamamideIrganox ® B 1171 31570-04-4 23128-74-7 1:1 Blend of Irganox ® 1098 andIrgafos ® 168 Irganox ® 1425 65140-91-2 Calciumbis(monoethyl(3,5-di-tert-butyl-4- hydroxybenzyl)phosphonate) Irganox ®3114 65140-91-2 Calcium bis(monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate) Irganox ® 3125 34137-09-23,5-Di-tert-butyl-4-hydroxy-hydrocinnamic acid triester with1,3,5-tris(2-hydroxyethyl)-S- triazine-2,4,6-(1H, 3H, 5H)-trioneIrgafos ® 168 31570-04-4 Tris(2,4-di-tert-butyl-phenyl)phosphite

Examples of reductive agents include sodium borohydride, hypophosphorousacid, Irgafos® 168, and mixtures thereof.

(E)-Bactericides

Examples of bactericides used in the compositions of this inventioninclude glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diolsold by Inolex Chemicals, located in Philadelphia, Pa., under the tradename Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-oneand 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company underthe trade name Kathon 1 to 1,000 ppm by weight of the agent.

(F)-Perfume

The present invention can contain a perfume. Suitable perfumes aredisclosed in U.S. Pat. No. 5,500,138, said patent being incorporatedherein by reference.

As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds.

Examples of perfume ingredients useful in the perfumes of the presentinvention compositions include, but are not limited to, hexyl cinnamicaldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate;terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol;2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol;3,7-dimethyl-trans-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol;3,7-dimethyl-1-octanol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

Additional examples of fragrance materials include, but are not limitedto, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil;dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate;beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;Schiffs base of4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methylanthranilate; cyclic ethyleneglycol diester of tridecandioic acid;3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;ionone beta; petitgrain; methyl cedrylone;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;16-hydroxy-9-hexadecenoic acid lactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol;5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexylacetate; patchouli; olibanum resinoid; labdanum; vetivert; copaibabalsam; fir balsam; and condensation products of hydroxycitronellal andmethyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehydeand indol; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehydeand methyl anthranilate.

More examples of perfume components are geraniol; geranyl acetate;linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellylacetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol;terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethylacetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzylbenzoate; styrallyl acetate; dimethylbenzylcarbinol;trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononylacetate; vetiveryl acetate; vetiverol;2-methyl-3-(p-tert-butylphenyl)-propanal;2-methyl-3-(p-isopropylphenyl)-propanal;3-(p-tert-butylphenyl)-propanal;4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal;n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehydedimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedrylmethylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methylionones; isomethyl ionomes; irones; cis-3-hexenol and esters thereof;indane musk fragrances; tetralin musk fragrances; isochroman muskfragrances; macrocyclic ketones; macrolactone musk fragrances; ethylenebrassylate.

The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

Perfume can be present at a level of from 0% to 10%, preferably from0.1% to 5%, and more preferably from 0.2% to 3%, by weight of thefinished composition. Fabric softener compositions of the presentinvention provide improved fabric perfume deposition.

Perfume ingredients may also be suitably added as releasable fragrances,for example, as pro-perfumes or pro-fragrances as described in U.S. Pat.No. 5,652,205 Hartman et al., issued Jul. 29, 1997, WO95/04809,WO96/02625, PCT US97/14610 filed 19 Aug. 1997 and claiming priority of19 Aug. 1996, and EP-A-0,752,465, incorporated herein by reference.

(G)-Enzyme

The compositions and processes herein can optionally employ one or moreenzymes such as lipases, proteases, cellulase, amylases and peroxidases.A preferred enzyme for use herein is a cellulase enzyme. Indeed, thistype of enzyme will further provide a color care benefit to the treatedfabric. Cellulases usable herein include both bacterial and fungaltypes, preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitablecellulases are also disclosed in WO 91/17243 to Novo, WO 96/34092, WO96/34945 and EP-A-0,739,982. In practical terms for current commercialpreparations, typical amounts are up to 5 mg by weight, more typically0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.Stated otherwise, the compositions herein will typically comprise from0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzymepreparation. In the particular cases where activity of the enzymepreparation can be defined otherwise such as with cellulases,corresponding activity units are preferred (e.g. CEVU or cellulaseEquivalent Viscosity Units). For instance, the compositions of thepresent invention can contain cellulase enzymes at a level equivalent toan activity from 0.5 to 1000 CEVU/gram of composition. Cellulase enzymepreparations used for the purpose of formulating the compositions ofthis invention typically have an activity comprised between 1,000 and10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.

Other Optional Ingredients

The present invention can include optional components conventionallyused in textile treatment compositions, for example: brighteners,chlorine scavengers such the non-polymeric one described inEP-A-0,841,391, colorants; surfactants; anti-shrinkage agents; fabriccrisping agents; spotting agents; germicides; fungicides; anti-oxidantssuch as butylated hydroxy toluene, anti-corrosion agents, antifoamagents, sun-protection agents such as described in EP-A-0,773,987, andthe like.

The present invention can also include other compatible ingredients,including those as disclosed in WO96/02625, WO96/21714, and WO96/21715,and dispersible polyolefin such as Velustrol® as disclosed in co-pendingapplication PCT/US 97/01644, and the like. The present invention canalso contain optional chelating agents such asethylenediamine-N,N′-disuccinic acid, (S,S) isomer in the form of itssodium salt (EDDS).

Still other various optional adjunct ingredients may also be used toprovide fully-formulated deteregent compositions. Typical of suchconventional deteresive ingredients include detersive surfactants,builders, bleaching compounds, and mixtures thereof, such as describedin WO 98/20098.

Form of the Composition

The colour care composition can take a variety of physical formsincluding liquid such as aqueous or non-aqueous compositions and solidforms such as solid particulate forms. Such compositions may be appliedonto a substrate such as a dryer sheet product, used as a rinse addedproduct, or as a spray or foam product.

Method of Use

In another aspect of the invention, there is provided a method forpreventing or reducing the colour fading of fabrics which comprises thesteps of contacting the fabric with a divalent salt or composition ofthe invention. Also herein provided is the use of said divalent salt toprevent or reduce the colour fading of fabrics.

By the present method and/use, it has surprisingly been found that thetreated fabric had better fabric appearance, especially in term of theircolor protection, compared to fabrics which had been treated with eitherno divalent salt.

Preferably, the method is performed in a domestic process. By “domesticprocess”, it is meant any step conventional to domestic laundering suchas soaking, washing, rinsing, and/or spraying as well as by means of adryer sheet onto which is adsorbed the composition.

Preferably, the contacting occurs in the step of a laundering process,preferably a rinse step of a laundry process, which more preferablyoccurs at a temperature range below 30° C., preferably between 5 and 25°C.

The invention is illustrated in the following non limiting examples, inwhich all percentages are on a weight basis unless otherwise stated.

In the examples, the abbreviated component identifications have thefollowing meanings: DEQA Di-(tallowyl-oxy-ethyl) dimethyl ammoniumchloride DOEQA Di-(oleyloxyethyl) dimethyl ammonium methylsulfate DTDMACDitallow dimethylammonium chloride DHEQA Di-(soft-tallowyl-oxy-ethyl)hydroxyethyl methyl ammonium methylsulfate DTDMAMS Ditallow dimethylammonium methylsulfate SDASA 1:2 Ratio of stearyldimethylamine:triple-pressed stearic acid Glycosperse S-20 Polyethoxylatedsorbitan monostearate available from Lonza Clay Calcium Bentonite Clay,Bentonite L, sold by Southern Clay Products PEG Polyethylene Glycol 4000PEI 1800 E1 Ethoxylated polyethylene imine (MW 1800, at 50% active) assynthesised in Synthesis example 1 PEI 1800 E3 Ethoxylated polyethyleneimine (MW 1800, at 50% active) as synthesised as per Synthesis example 1PEI 1200 E1 Ethoxylated polyethylene imine (MW 1200, at 50% active inwater) as synthesised in Synthesis example 2 PEI 1200 E4 Ethoxylatedpolyethylene imine (MW 1200, at 50% active in water) as synthesised perSynthesis example 2 Dye Fix 1 Cellulose reactive dye fixing agentavailable under the tradename Indosol CR from Clariant Dye Fix 2Cellulose reactive dye fixing agent available under the tradename RewinWBS from CHT R. Beitlich Divalent salt 1 Magnesium sulphate Divalentsalt 2 Magnesium chloride Divalent salt 3 Calcium chloride LAS Sodiumlinear C₁₁₋₁₃ alkyl benzene sulfonate CxyAS Sodium C_(1x)-C_(1y) alkylsulfate CxyEzS Sodium C_(1x)-C_(1y) alkyl sulfate condensed with z molesof ethylene oxide CxyEz C_(1x)-C_(1y) predominantly linear primaryalcohol condensed with an average of z moles of ethylene oxide APAC₈-C₁₀ amido propyl dimethyl amine CFAA C₁₂-C₁₄ (coco) alkyl N-methylglucamide TFAA C₁₆-C₁₈ alkyl N-methyl glucamide TPKFA C₁₂-C₁₄ toppedwhole cut fatty acids Citric acid Anhydrous citric acid Borate Sodiumborate Protease Proteolytic enzyme, having 3.3% by weight of activeenzyme, sold by NOVO Industries A/S under the tradename SavinaseAlcalase Proteolytic enzyme, having 5.3% by weight of active enzyme,sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having 0.23% byweight of active enzyme, sold by NOVO Industries A/S under the tradenameCarezyme Amylase Amylolytic enzyme, having 1.6% by weight of activeenzyme, sold by NOVO Industries A/S under the tradename Termamyl 120TLipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold byNOVO Industries A/S under the tradename Lipolase Endolase Endoglucanaseenzyme, having 1.5% by weight of active enzyme, sold by NOVO IndustriesA/S DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triaminepenta (methylene phosphonate), marketed by Monsanto under the TradenameDequest 2060 Brightener 1 Disodium 4,4′-bis(2-sulphostyryl)biphenylBrightener 2 Disodium 4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2′-disulfonate HEDP 1,1-hydroxyethane diphosphonicacid TEPAE Tetraethylenepentaamine ethoxylate PVNO PolyvinylpyridineN-oxide polymer, with an average molecular weight of 50,000 SRP 1Anionically end capped poly esters SRP 2 Diethoxylated poly (1, 2propylene terephtalate) short block polymer Silicone antifoamPolydimethylsiloxane foam controller with siloxane- oxyalkylenecopolymer as dispersing agent with a ratio of said foam controller tosaid dispersing agent of 10:1 to 100:1 Opacifier Water based monostyrenelatex mixture, sold by BASF Aktiengesellschaft under the tradenameLytron 621 Polycarboxylic Polycarboxylic compound marketed by BASF underthe tradename Sokalan CP 10 Glycolic Glycolic acid Polymer IPolyvinylpyrrolidone K90 available under the tradename Luviskol K90 fromBASF. Bayhibit AM 2-phosphonobutane-1,2,4-tricarboxylic acidcommercially available from Bayer pH Measured as a 1% solution indistilled water at 20° C.

SYNTHESIS EXAMPLE 1 Preparation of PEI 1800 E₁

Step A)-The ethoxylation is conducted in a 2 gallon stirred stainlesssteel autoclave equipped for temperature measurement and control,pressure measurement, vacuum and inert gas purging, sampling, and forintroduction of ethylene oxide as a liquid. A ˜20 lb. net cylinder ofethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid bya pump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.

A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, EpominSP-018 having a listed average molecular weight of 1800 equating to0.417 moles of polymer and 17.4 moles of nitrogen functions) is added tothe autoclave. The autoclave is then sealed and purged of air (byapplying vacuum to minus 28″ Hg followed by pressurization with nitrogento 250 psia, then venting to atmospheric pressure). The autoclavecontents are heated to 130° C. while applying vacuum. After about onehour, the autoclave is charged with nitrogen to about 250 psia whilecooling the autoclave to about 105° C. Ethylene oxide is then added tothe autoclave incrementally over time while closely monitoring theautoclave pressure, temperature, and ethylene oxide flow rate. Theethylene oxide pump is turned off and cooling is applied to limit anytemperature increase resulting from any reaction exotherm. Thetemperature is maintained between 100 and 110° C. while the totalpressure is allowed to gradually increase during the course of thereaction. After a total of 750 grams of ethylene oxide has been chargedto the autoclave (roughly equivalent to one mole ethylene oxide per PEInitrogen function), the temperature is increased to 110° C. and theautoclave is allowed to stir for an additional hour. At this point,vacuum is applied to remove any residual unreacted ethylene oxide.

Step B)- The reaction mixture is then deodorized by passing about 100cu. ft. of inert gas (argon or nitrogen) through a gas dispersion fritand through the reaction mixture while agitating and heating the mixtureto 130° C.

The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen.

In other preparations the neutralization and deodorization isaccomplished in the reactor before discharging the product.

If a PEI 1800 E₇ is desired, the following step of catalyst additionwill be included between Step A and B.

Vacuum is continuously applied while the autoclave is cooled to about50° C. while introducing 376 g of a 25% sodium methoxide in methanolsolution (1.74 moles, to achieve a 10% catalyst loading based upon PEInitrogen functions). The methoxide solution is sucked into the autoclaveunder vacuum and then the autoclave temperature controller setpoint isincreased to 130° C. A device is used to monitor the power consumed bythe agitator. The agitator power is monitored along with the temperatureand pressure. Agitator power and temperature values gradually increaseas methanol is removed from the autoclave and the viscosity of themixture increases and stabilizes in about 1 hour indicating that most ofthe methanol has been removed. The mixture is further heated andagitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105° C. while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4500 g of ethylene oxide (resulting in a total of7 moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110° C. and themixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167 g methanesulfonic acid (1.74 moles).

Other preferred examples such as PEI 1800 E3, PEI 1800 E4, PEI 1800 E15and PEI 1800 E20 can be prepared by the above method by adjusting thereaction time and the relative amount of ethylene oxide used in thereaction.

SYNTHESIS EXAMPLE 2 Preparation of PEI 1200 E₁

Step A)-The ethoxylation is conducted in a 2 gallon stirred stainlesssteel autoclave equipped for temperature measurement and control,pressure measurement, vacuum and inert gas purging, sampling, and forintroduction of ethylene oxide as a liquid. A ˜20 lb. net cylinder ofethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid bya pump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.

A 750 g portion of polyethyleneimine (PEI) ( having a listed averagemolecular weight of 1200 equating to about 0.625 moles of polymer and17.4 moles of nitrogen functions) is added to the autoclave. Theautoclave is then sealed and purged of air (by applying vacuum to minus28″ Hg followed by pressurization with nitrogen to 250 psia, thenventing to atmospheric pressure). The autoclave contents are heated to130° C. while applying vacuum. After about one hour, the autoclave ischarged with nitrogen to about 250 psia while cooling the autoclave toabout 105° C. Ethylene oxide is then added to the autoclaveincrementally over time while closely monitoring the autoclave pressure,temperature, and ethylene oxide flow rate. The ethylene oxide pump isturned off and cooling is applied to limit any temperature increaseresulting from any reaction exotherm. The temperature is maintainedbetween 100 and 110° C. while the total pressure is allowed to graduallyincrease during the course of the reaction. After a total of 750 gramsof ethylene oxide has been charged to the autoclave (roughly equivalentto one mole ethylene oxide per PEI nitrogen function), the temperatureis increased to 110° C. and the autoclave is allowed to stir for anadditional hour. At this point, vacuum is applied to remove any residualunreacted ethylene oxide.

Step B)- The reaction mixture is then deodorized by passing about 100cu. ft. of inert gas (argon or nitrogen) through a gas dispersion fritand through the reaction mixture while agitating and heating the mixtureto 130° C.

The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen.

In other preparations the neutralization and deodorization isaccomplished in the reactor before discharging the product.

If a PEI 1200 E₇ is desired, the following step of catalyst additionwill be included between Step A and B.

Vacuum is continuously applied while the autoclave is cooled to about50° C. while introducing 376 g of a 25% sodium methoxide in methanolsolution (1.74 moles, to achieve a 10% catalyst loading based upon PEInitrogen functions). The methoxide solution is sucked into the autoclaveunder vacuum and then the autoclave temperature controller setpoint isincreased to 130° C. A device is used to monitor the power consumed bythe agitator. The agitator power is monitored along with the temperatureand pressure. Agitator power and temperature values gradually increaseas methanol is removed from the autoclave and the viscosity of themixture increases and stabilizes in about 1 hour indicating that most ofthe methanol has been removed. The mixture is further heated andagitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105° C. while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4500 g of ethylene oxide (resulting in a total of7 moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110° C. and themixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167 g methanesulfonic acid (1.74 moles).

Other preferred examples such as PEI 1200 E2, PEI 1200 E4, PEI 1200 E15and PEI 1200 E20 can be prepared by the above method by adjusting thereaction time and the relative amount of ethylene oxide used in thereaction.

EXAMPLE 1

The following fabric care compositions are in accordance with thepresent invention Active (levels in %) I II III IV V VI VII PEI 1200 E110  9 8 7 6 2 4 Dye fix 2   2.5   2.5 1 2 3 2 3 Divalent salt 1 5 6 7 810  2 15  DEQA — — — — — 25  — HEDP 1   0.2   0.4   0.5   0.5   0.1 1ammonium chloride — — — — — —   0.25 SRP1 — — — — — — 2 Water and minorsto balance to 100 Active (levels in %) VIII IX X XI XII XIII XIV PEI1200 E4 10  9 8 7 6 2 4 Dye fix 1   2.5   2.5 1 2 3 2 3 Divalent salt 25 6 7 8 10  2 15  DTDMAC 25  HEDP 1   0.2   0.4   0.5   0.5   0.1 1ammonium chloride — — — — — —   0.25 SRP1 — — — — — — 2 Water and minorsto balance to 100 XV XVI XVII XVIII Divalent salt 1 5 15   2   2   PEI1800 E4 — — 15   — Polymer I — — — 5   DEQA 5 — — — Dye fix 1 — 2.5 — —Bayhibit AM 2 — — — Cellulase — 0.1 — 0.5 Perfume   0.15 0.3 0.1 0.4Water and minors Balance Balance Balance Balance

EXAMPLE 2

The following compositions for use as dryer-added sheets are inaccordance with the invention I II III IV V VI DOEQA 40   25   — — — —DHEQA — — 20   — — — DTDMAMS — — — 20   12   60   SDASA 30   30   20  30   20   — Glycosperse S-20 — — 10   — — — Glycerol — — — 20   10   —Monostearate Clay 4   4   3   4   4   — Perfume 0.7 1.1 0.7 1.6 2.6 1.4PEI 1800 E1 — 5   — — — — PEI 1200 E1 — — 4   2.2 — — PEI 1800 E3 2   —— — 5   7.0 Dye fix 2 2   5   4   2.2 5   3   Divalent salt 1 5   3  10   2   5   6   HEDP 0.2 — 0.5 — — 0.7 Glycolic — 0.2 — 0.2 — —Polycarboxylic — 0.2 — — 0.4 — Stearic acid to balance

EXAMPLE 3

The following liquid detergent formulations were prepared in accord withthe invention (levels are given as parts per weight). I II III IV V LAS11.5  8.8 — 3.9 — C25E2.5S — 3.0 18.0  — 16.0  C45E2.25S 11.5  3.0 —15.7  — C23E9 — 2.7 1.8 2.0 1.0 C23E7 3.2 — — — — CFAA — — 5.2 — 3.1TPKFA 1.6 — 2.0 0.5 2.0 Citric acid (50%) 6.5 1.2 2.5 4.4 2.5 Calciumformate 0.1  0.06 0.1 — — Sodium formate 0.5  0.06 0.1  0.05  0.05Sodium cumene sulfonate 4.0 1.0 3.0  1.18 — Borate 0.6 — 3.0 2.0 2.9Sodium hydroxide 5.8 2.0 3.5 3.7 2.7 Ethanol  1.75 1.0 3.6 4.2 2.9 1,2propanediol 3.3 2.0 8.0 7.9 5.3 Monoethanolamine 3.0 1.5 1.3 2.5 0.8TEPAE 1.6 — 1.3 1.2 1.2 Protease 1.0 0.3 1.0 0.5 0.7 Lipase — — 0.1 — —Cellulase — — 0.1 0.2  0.05 Amylase — — — 0.1 — SRP1 0.2 — 0.1 — — DTPA— — 0.3 — — Divalent salt 1 2   3   4   5   4   PVNO — — 0.3 — 0.2Perfume 0.4 0.4 0.4 0.4 0.4 Brightener 1 0.2  0.07 0.1 — — Siliconeantifoam  0.04  0.02 0.1 0.1 0.1 Water/minors

EXAMPLE 4

The following liquid detergent formulations were prepared in accord withthe invention (levels are given in parts per weight): I II III IV V VIVII VIII LAS 10.0  13.0  9.0 — 25.0  — — — C25AS 4.0 1.0 2.0 10.0  —13.0  18.0  15.0  C25E3S 1.0 — — 3.0 — 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 — — 4.0 4.0 TFAA — — — 4.5 — 6.0 8.0 8.0 APA — 1.4 — — 3.0 1.0 2.0 —TPKFA 2.0 — 13.0  7.0 — 15.0  11.0  11.0  Citric acid 2.0 3.0 1.0 1.51.0 1.0 1.0 1.0 Dodecenyl/tetradecenyl 12.0  10.0  — — 15.0  — — —succinic acid Rape seed fatty acid 4.0 2.0 1.0 — 1.0 — 3.5 — Ethanol 4.04.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.010.0  13.0  Monoethanolamine — — — 5.0 — — 9.0 9.0 Triethanolamine — —8.0 — — — — — TEPAE 0.5 — 0.5 0.2 — — 0.4 0.3 DTPMP 1.0 1.0 0.5 1.0 2.01.2 1.0 — Divalent salt 2 2   3   4   5   4   5   5   5   Protease 0.50.5 0.4  0.25 — 0.5 0.3 0.6 Alcalase — — — — 1.5 — — — Lipase —  0.10 — 0.01 — —  0.15  0.15 Amylase  0.25  0.25 0.6 0.5  0.25 0.9 0.6 0.6Cellulase — — —  0.05 — —  0.15  0.15 Endolase — — —  0.10 — —  0.07 —SRP2 0.3 — 0.3 0.1 — — 0.2 0.1 Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.52.5 Calcium chloride —  0.02 —  0.01 — — — — Bentonite clay — — — — 4.04.0 — — Brightener 1 — 0.4 — — 0.1 0.2 0.3 — Sud supressor 0.1 0.3 — 0.10.4 — — — Opacifier 0.5 0.4 — 0.3 0.8 0.7 — — Perfume — 0.2 0.2 0.4 0.40.4 0.4 0.4 Water/minors NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2

EXAMPLE 5

The following liquid detergent compositions were prepared in accord withthe invention (levels are given in parts per weight). I II LAS 27.6 18.9 C45AS 13.8  5.9 C13E8 3.0 3.1 Oleic acid 3.4 2.5 Citric acid 5.45.4 Sodium hydroxide 0.4 3.6 Calcium formate 0.2 0.1 Sodium formate —0.5 Ethanol 7.0 — Monoethanolamine 16.5  8.0 1,2 propanediol 5.9 5.5Xylene sulfonic acid — 2.4 TEPAE 1.5 0.8 Protease 1.5 0.6 PEG — 0.7Brightener 2 0.4 0.1 Perfume 0.5 0.3 Divalent salt 1 3   3 Water/minors

1. A colour care composition comprising: i) a dye fixing agent, and ii)a divalent salt.
 2. A composition according to claim 1, wherein said dyefixing agent is a cationic dye fixing agent.
 3. A composition accordingto claim 1, wherein said dye fixing agent is cellulose reactive dyefixing agent.
 4. A composition according to claim 3, wherein thecellulose reactive dye fixing agent is a product containing the reactivegroup of the reactive dye classes selected from halogeno-triazineproducts, vinyl sulphones compounds, epichlorhydrine derivatives,hydroxyethylene urea derivatives, formaldehyde condensation products,polycarboxylates, glyoxal and glutaraldehyde derivatives and mixturesthereof.
 5. A composition according to claim 4, wherein said cellulosereactive dye fixing agent is a formaldehyde condensation productselected from the condensation products derived from formaldehyde and agroup selected from an amino-group, an imino-group, a phenol group, anurea group, a cyanamide group and an aromatic group.
 6. A compositionaccording to claim 1, wherein said dye fixing agent is present in anamount of 0.01% to 50% by weight of the composition.
 7. A compositionaccording to claim 1, wherein said divalent salt is made of earthalkaline metal salts.
 8. A composition according to claim 7, whereinsaid divalent salt is made of earth alkaline metal salts selected frommagnesium, calcium and mixtures thereof.
 9. A composition according toclaim 1, wherein said divalent salt is selected from magnesium sulphate,magnesium bicarbonate, magnesium chloride, magnesium borate, magnesiumcitrate, and mixtures thereof.
 10. A composition according to claim 9,wherein said divalent salt is selected from magnesium sulphate,magnesium chloride and mixtures thereof.
 11. A composition according toclaim 1, wherein said divalent salt is present in an amount of from0.01% to 90% by weight of the composition.
 12. A composition accordingto claim 11, wherein said divalent salt is present in an amount of from0.5% to 90% by weight of the composition.
 13. A composition according toclaim 12, wherein said divalent salt is present in an amount of from 1%to 20% by weight of the composition.
 14. A composition according toclaim 13, wherein said divalent salt is present in an amount of from 3%to 10% by weight of the composition.
 15. A method for preventing orreducing the colour fading of fabrics which comprises the steps ofcontacting the fabric with a divalent salt or composition as defined inclaim
 1. 16. A method according to claim 15, wherein said method isperformed in a domestic process.
 17. A method according to claim 16,wherein said method is performed in a rinse process.